Ortho-alkylation of aromatic amines

Abstract

A catalytic intermediate useful in the preparation of ortho-alkylated aromatic amines is prepared by heating an amine in the presence of aluminum metal, zinc metal and aluminum chloride. This catalytic intermediate is used to alkylate aromatic amines which may be the same as or different from the amine used in the catalytic intermediate preparation. In a preferred embodiment, toluenediamine is alkylated in the ortho positions to form diethyltoluenediamine.

What is claimed is: 
     
       1. A process for the preparation of ortho-alkylated amines comprising preparing a catalytic intermediate by heating a first aromatic amine with (1)aluminum:   (2)aluminum chloride;   (3)zinc, having a particle size in the range of from about 20 to 200 mesh, U.S. Standard; and   (4)optionally, a solvent and subsequently reacting the catalytic intermediate with an alkene and, optionally, a second aromatic amine at elevated temperature and pressure under reaction conditions sufficient to produce the ortho-alkylated aromatic amines.   
     
     
       2. The process of claim 1 wherein the first aromatic amine and the second aromatic amine are phenylenediamines. 
     
     
       3. The process of claim 2 wherein the phenylenediamines are selected from the group consisting of toluenediamine, diethyltoluenediamine and mixtures thereof. 
     
     
       4. The process of claim 1 wherein the first aromatic amine and the second aromatic amine are the same. 
     
     
       5. The process of claim 1 wherein the first aromatic amine and the second aromatic are different. 
     
     
       6. The process of claim 1 wherein the alkene contains from about two to about six carbon atoms. 
     
     
       7. The process of claim 6 wherein the alkene is selected from the group consisting of ethene, propene, butene and mixtures thereof. 
     
     
       8. The process of claim 7 wherein the alkene is ethene. 
     
     
       9. The process of claim 1 wherein the reaction of the alkene is carried out at a pressure in the range of about 250 to about 1000 psig. 
     
     
       10. The process of claim 1 wherein the catalytic intermediate preparation and the reaction of the alkene with the catalyst are carried out in different reactors. 
     
     
       11. The process of claim 1 wherein the catalytic intermediate preparation and the reaction of the alkene with the catalyst are carried out in different reactors. 
     
     
       12. The process of claim 11 wherein the catalytic intermediate is prepared in a glass lined reactor and the reaction of the alkene with the catalytic intermediate is carried out in a carbon steel reactor. 
     
     
       13. A process for the preparation of diethyltoluenediamine comprising preparing a catalytic intermediate by heating a first aromatic amine selected from the group consisting of toluenediamine, diethyltoluenediamine and mixtures thereof with (1) aluminum;   (2) aluminum chloride;   (3) zinc, having a particle size in the range of from about 20 to 200 mesh, U.S. Standard; and   (4) optionally, a solvent and subsequently reacting the catalytic intermediate with ethene and toluenediamine.